CN101954295B - Catalyst system for synthesizing acetic acid by methanol low-pressure carbonyl and application thereof - Google Patents
Catalyst system for synthesizing acetic acid by methanol low-pressure carbonyl and application thereof Download PDFInfo
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title claims abstract description 179
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 151
- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 20
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 238000005810 carbonylation reaction Methods 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229940071870 hydroiodic acid Drugs 0.000 claims abstract description 18
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 14
- 150000001351 alkyl iodides Chemical class 0.000 claims abstract description 7
- 239000002798 polar solvent Substances 0.000 claims abstract description 5
- 230000006315 carbonylation Effects 0.000 claims description 30
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 29
- 239000010948 rhodium Substances 0.000 claims description 23
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 17
- 239000011630 iodine Substances 0.000 claims description 17
- 229910052740 iodine Inorganic materials 0.000 claims description 17
- 229910052783 alkali metal Inorganic materials 0.000 claims description 12
- -1 alkali metal salt Chemical class 0.000 claims description 12
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 12
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 9
- 150000003283 rhodium Chemical class 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- 229910052703 rhodium Inorganic materials 0.000 claims description 6
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 5
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 4
- 239000003426 co-catalyst Substances 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 150000003284 rhodium compounds Chemical class 0.000 abstract description 3
- 229910001516 alkali metal iodide Inorganic materials 0.000 abstract 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 18
- 229910002091 carbon monoxide Inorganic materials 0.000 description 18
- 238000000034 method Methods 0.000 description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 229910052726 zirconium Inorganic materials 0.000 description 8
- 230000008569 process Effects 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- RHZBHKVBAKQJLM-UHFFFAOYSA-N C(=O)=CC(=O)O.CO Chemical compound C(=O)=CC(=O)O.CO RHZBHKVBAKQJLM-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000004354 sulfur functional group Chemical group 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A catalyst system for synthesizing acetic acid by low-pressure methanol carbonyl is prepared from rhodium compound as active component of catalyst, alkyl iodide, water, hydroiodic acid, alkali-metal iodide and sulfonate as cocatalyst, and acetic acid as polar solvent. The catalyst system is added with sulfonate, and has better catalytic activity and stability. In the methanol carbonylation reaction, the system can convert methanol into acetic acid at high speed and high selectivity under lower temperature and pressure. The reaction reduces the concentration of water and hydroiodic acid, and the corrosiveness to equipment is reduced.
Description
Technical field
The present invention relates to a kind of catalyst system and application thereof that is used for catalysis methanol low pressure carbonyl synthesis acetic acid.
Background technology
The industrialized preparing process of acetic acid has acetaldehyde oxidation, butane or light oil liquid phase oxidation, methanol carbonylation.Low-pressure methanol carbonylation method wherein has that flow process is simple, reaction condition is gentle, selectivity is good, low power consumption and other advantages, has become the most competitive in the world production of acetic acid method at present, also is acetic acid synthesized in the world main production route at present.In addition, material benzenemethanol is in liberal supply and with low cost, and has the atomic economy reaction characteristic that total overall reaction thing molecule generates whole purpose product molecules, when having reduced the accessory substance environmental pollution, the coordinated development of economy and environmental protection is had great significance.
In carbonylation of methanol synthesis process route, the research of catalyst is an important content.Purpose is to study active high, good stability, is easy to reclaim, and has the novel catalyst system of homogeneous phase and heterogeneous two types of catalyst advantages concurrently.Research for many years mainly concentrates on these several aspects of base metal, part, carrier and auxiliary agent, and the purpose of its research is to improve existing activity of such catalysts and stability, reaches the raising reaction rate, increases the purpose of acetic acid productive rate.
Mostly the activated centre that existing industrial carbonylation is produced the acetic acid catalyst system and catalyzing is [Rh (CO)
2I
2]
-, for a long time, further improve [Rh (CO)
2I
2]
-As the stability of catalytic active species in reaction, and reduce the water content in the reaction system, be one of important contents of methanol carbonyl synthesized acetic acid catalyst research, and obtained certain progress.Wherein comparatively effective method is with the little molecule that contains nitrogen, phosphorus, oxygen, sulphur functional group or macromolecule ligand and Rh formation complex, reaches the purpose of improving rhodium active specy stability, improving its catalytic activity.For example, (CN100750, US5281359 US6458996), make catalyst when keeping higher carbonylation activity, and heat endurance also is improved as the part of catalyst to adopt high polymer.
In numerous all kinds of catalyst researches; The selection of reactive metal is except that rhodium; Many transition metal such as iridium, ruthenium, nickel, cobalt are all studied, and certain progress are also arranged, wherein with iridium catalyst system and catalyzing (EP849249; US5672743) best results, the reactivity worth of catalyst has had great improvement.
Adopt metal salt stabilizers to improve the research of rhodium catalyst system and catalyzing performance, also quite become effective.For example; (EP 0161874; JP60-239434) through adding the salt compounded of iodine of high level alkali metal (lithium or sodium), improved the stability of catalyst, and accelerated the oxidation addition speed (the speed control step of reaction) of MeI to a certain extent; Reduced the water content in the Processes for Producing Acetic Acid simultaneously, wherein particularly remarkable with the promoting catalysis of lithium iodide.Effect through salt compounded of iodine can than obtain under the low water content with high water content under identical reactivity, improved the utilization ratio of CO.But produce in the catalystic converter system of acetic acid at the high iodine concentration of this type, possibly cause the concentration of residual iodine in the product acid higher, and then can for example cause poisoning of catalyst in the preparation of VAM in downstream product.
Except the alkali metal salt compounded of iodine; To other different types of catalytic promoters and transition metal salt Study of Stabilizers; Good progress is all arranged; Used the LiI stabilizing agent to be aided with the group vib slaine like US5218143, promptly adopting the acetate of lower valency molybdenum, chromium, tungsten or salt compounded of iodine is co-catalyst, or with Mo (CO)
6, W (CO)
6, Cr (CO)
6Carbonyls is a co-stabilizer, in the reaction of acetic acid synthesis from methanol carbonylation, has obtained result preferably.
Though the catalyst structure pattern in the existing suitability for industrialized production has catalytic activity preferably, when high temperature, low CO dividing potential drop, be prone to be converted into trivalent rhodium anionic complex, and then generate deposition and lose activity.In addition; Be to increase the dissolubility of catalyst in the production of acetic acid process, need reaction system to keep higher water and hydroiodic acid content so that the maintenance system high reaction activity and high (EP55618, EP161874); But therefore quickened water gas reaction; Consumed the raw material carbon monoxide, the severe corrosive of medium has improved the requirement to equipment material simultaneously, and the big water gaging that exists in the system has increased the complexity of product postprocessing operation.Catalyst system and catalyzing among the present invention has overcome some weakness of existing catalyst preferably.
Summary of the invention
The object of the present invention is to provide a kind of catalyst system and application thereof of synthesizing acetic acid by methanol low-pressure carbonylation, this system can be high-speed, highly selective is acetic acid with methanol conversion under lower temperature and pressure.Reaction has reduced the concentration of water and hydroiodic acid, and corrosion on Equipment property is reduced.
For realizing above-mentioned purpose; The catalyst system of synthesizing acetic acid by methanol low-pressure carbonylation provided by the invention; As the activity of such catalysts thing, add alkyl iodide, water, hydroiodic acid, alkali metal salt compounded of iodine and sulfonate with rhodium salt, and be aided with polar solvent and form as co-catalyst; Wherein:
The consumption of rhodium salt is counted 200-1000ppm with rhodium by weight percentage;
The content of alkyl iodide in reaction system is 5%-18% by weight percentage;
The concentration of water is 4%-6% by weight percentage;
The concentration of hydroiodic acid is 0.2%-0.4% by weight percentage;
The concentration of alkali metal salt compounded of iodine is 7%-12% by weight percentage;
The mol ratio of sulfonate and rhodium salt is 1-100.
In the catalyst system of described synthesizing acetic acid by methanol low-pressure carbonylation, used rhodium salt is: RhCl
3, RhBr
3, RhI
3, Rh (OAc)
2, [Rh (CO)
2Cl]
2, [Rh (CO)
2Br]
2Or [Rh (CO)
2I]
2
In the catalyst system of described synthesizing acetic acid by methanol low-pressure carbonylation, used alkyl iodide is an iodomethane.
In the catalyst system of described synthesizing acetic acid by methanol low-pressure carbonylation, used alkali metal salt compounded of iodine is a lithium iodide.
In the catalyst system of described synthesizing acetic acid by methanol low-pressure carbonylation, used sulfonate is Zn, ammonium and alkali-metal sulfonate.
In the catalyst system of described synthesizing acetic acid by methanol low-pressure carbonylation, used alkali metal sulfonate is LiHSO
3, NaHSO
3, KHSO
3Or their salt that contains the crystallization water.
In the catalyst system of described synthesizing acetic acid by methanol low-pressure carbonylation, the used Zn or the sulfonate of ammonium are respectively Zn (HSO
3)
2, NH
4HSO
3Or their salt that contains the crystallization water.
In the catalyst system of described synthesizing acetic acid by methanol low-pressure carbonylation, when catalyzed carbonylation prepared acetic acid, reactant was a methyl alcohol.
In the catalyst system of described synthesizing acetic acid by methanol low-pressure carbonylation, used polar solvent is an acetic acid, and its consumption is the 10-120% of reaction-ure mixture by weight.
When above-mentioned catalyst system provided by the invention is used in the synthetic preparation of low-pressure methanol carbonyl acetic acid; Carry out through in reactor, adding following ingredients: (I) methyl alcohol is as the raw material of reaction, (II) rhodium compound, (III) iodomethane, water, hydroiodic acid; (IV) lithium iodide; (V) sulfonate, (VI) acetate solvate, (VII) led to carbon monoxide.Reaction temperature is 160-190 ℃, and reaction pressure is 2.8-3.2MPa, and the reaction time is 0.1-0.5 hour.
The principal character of catalyst system provided by the invention is:
1, alkali metal salt compounded of iodine in this catalyst system and sulfonate all have stabilization to catalyst, make that the stability of catalyst is better, and operating mode scope applicatory is wideer, helps the adjustment and the optimization of production technology.
2, alkali metal salt compounded of iodine in this catalyst system and sulfonate are all benefited to improving activity of such catalysts.The dissolubility of lithium iodide in reaction medium is better, but too much lithium iodide can make the content of iodine in the system too high, and this follow-up iodine that removes for product has brought trouble.The addition of sulfonate in system is less relatively, but bigger to improving the activity of such catalysts contribution, this has alleviated the too high problem of content of iodine in the system to a certain extent.
3, reduced the concentration of water and hydroiodic acid in the reaction system, this separating technology for follow-up acetic acid and water provides great facility, and has reduced corrosion on Equipment.
4, this reaction system is under lower temperature and pressure, can be high-speed, highly selective is acetic acid with methanol conversion.
5, prepare in the reaction system of acetic acid in the catalyst carbonylation of methanol that the present invention relates to, acetic acid content is between the 10-120% (wt) of reaction medium.Acetic acid is a kind of excellent solvent; Can not only make in the reaction system chemofacies dissolubility between each main component can be better; And can increase the solubility of catalyst in reaction medium, also carbonylation is had and significantly induce and facilitation, so help the raising of rate of catalysis reaction.
6, prepare in the reaction system of acetic acid in the catalyst carbonylation of methanol that the present invention relates to, need not carry out the catalyst precarsor preliminary treatment of any complicacy, the formation of catalyst system and catalyzing is simple rapidly, catalytic process is convenient and easy.
The specific embodiment
Embodiment 1
In 250mL zirconium matter autoclave pressure, add [Rh (CO)
2Cl]
20.150g, methyl alcohol 0.79mol, acetic acid 0.83mol, iodomethane 0.10mol, water 4%, hydroiodic acid 0.2%, lithium iodide 8.0g, LiHSO
30.3g.
Behind twice of the air in the carbon monoxide replacement reaction kettle, charge into carbon monoxide and seal this system to system, setting mixing speed is 500 rev/mins, 170 ℃ of reaction temperatures, reaction pressure keeps 3.0MPa, and the reaction time is 18min.Methanol conversion 99.0%, acetic acid space-time yield are 21.2molAcOH/ (Lh).
Embodiment 2
In 250mL zirconium matter autoclave pressure, add Rh (OAc)
20.160g, methyl alcohol 0.79mol, acetic acid 0.83mol, iodomethane 0.12mol, water 4%, hydroiodic acid 0.3%, lithium iodide 8.0g, NaHSO
30.3g.
Behind twice of the air in the carbon monoxide replacement reaction kettle, charge into carbon monoxide and seal this system to system, setting mixing speed is 500 rev/mins, 170 ℃ of reaction temperatures, reaction pressure keeps 3.2MPa, and the reaction time is 20min.Methanol conversion 99.1%, acetic acid space-time yield are 19.8molAcOH/ (Lh).
Embodiment 3
In 250mL zirconium matter autoclave pressure, add RhBr
30.330g, methyl alcohol 0.72mol, acetic acid 0.83mol, iodomethane 0.10mol, water 5%, hydroiodic acid 0.2%, lithium iodide 8.0g, LiHSO
30.3g.
Behind twice of the air in the carbon monoxide replacement reaction kettle, charge into carbon monoxide and seal this system to system, setting mixing speed is 500 rev/mins, 170 ℃ of reaction temperatures, reaction pressure keeps 3.0MPa, and the reaction time is 21min.Methanol conversion 98.8%, acetic acid space-time yield are 18.5molAcOH/ (Lh).
Embodiment 4
In 250mL zirconium matter autoclave pressure, add [Rh (CO)
2I]
20.210g, methyl alcohol 0.79mol, acetic acid 0.83mol, iodomethane 0.08mol, water 6%, hydroiodic acid 0.2%, lithium iodide 8.0g, NH
4HSO
30.3g.
Behind twice of the air in the carbon monoxide replacement reaction kettle, charge into carbon monoxide and seal this system to system, setting mixing speed is 500 rev/mins, 170 ℃ of reaction temperatures, reaction pressure keeps 2.8MPa, and the reaction time is 15min.Methanol conversion 99.0%, acetic acid space-time yield are 17.4molAcOH/ (Lh).
Embodiment 5
In 250mL zirconium matter autoclave pressure, add Rh (OAc)
20.144g, methyl alcohol 0.79mol, acetic acid 0.83mol, iodomethane 0.08mol, water 4%, hydroiodic acid 0.4%, lithium iodide 8.0g, KHSO
30.3g.
Behind twice of the air in the carbon monoxide replacement reaction kettle, charge into carbon monoxide and seal this system to system, setting mixing speed is 500 rev/mins, 170 ℃ of reaction temperatures, reaction pressure keeps 3.2MPa, and the reaction time is 20min.Methanol conversion 99.0%, acetic acid space-time yield are 19.4molAcOH/ (Lh).
Embodiment 6
In 250mL zirconium matter autoclave pressure, add Rh (OAc)
20.144g, methyl alcohol 0.79mol, acetic acid 0.83mol, iodomethane 0.08mol, water 5%, hydroiodic acid 0.3%, lithium iodide 8.0g, LiHSO
30.3g.
Behind twice of the air in the carbon monoxide replacement reaction kettle, charge into carbon monoxide and seal this system to system, setting mixing speed is 500 rev/mins, 170 ℃ of reaction temperatures, reaction pressure keeps 2.8MPa, and the reaction time is 25min.Methanol conversion 99.1%, acetic acid space-time yield are 20.1molAcOH/ (Lh).
Embodiment 7
In 250mL zirconium matter autoclave pressure, add [Rh (CO)
2Cl]
20.150g, methyl alcohol 0.79mol, acetic acid 0.83mol, iodomethane 0.10mol, water 5%, hydroiodic acid 0.4%, lithium iodide 8.0g, NH
4HSO
30.3g.
Behind twice of the air in the carbon monoxide replacement reaction kettle, charge into carbon monoxide and seal this system to system, setting mixing speed is 500 rev/mins, 170 ℃ of reaction temperatures, reaction pressure keeps 3.0MPa, and the reaction time is 18min.Methanol conversion 98.9%, acetic acid space-time yield are 17.2molAcOH/ (Lh).
Embodiment 8
In 250mL zirconium matter autoclave pressure, add RhI
30.330g, methyl alcohol 0.72mol, acetic acid 0.83mol, iodomethane 0.10mol, water 6%, hydroiodic acid 0.3%, lithium iodide 8.0g, Zn (HSO
3)
20.3g.
Behind twice of the air in the carbon monoxide replacement reaction kettle, charge into carbon monoxide and seal this system to system, setting mixing speed is 500 rev/mins, 170 ℃ of reaction temperatures, reaction pressure keeps 3.0MPa, and the reaction time is 21min.Methanol conversion 98.8%, acetic acid space-time yield are 16.5molAcOH/ (Lh).
Claims (7)
1. the catalyst system of a synthesizing acetic acid by methanol low-pressure carbonylation as the activity of such catalysts thing, adds alkyl iodide, water, hydroiodic acid, alkali metal salt compounded of iodine and sulfonate as co-catalyst with rhodium salt, and is aided with polar solvent and forms, and it is characterized in that:
The consumption of rhodium salt is counted 200-1000ppm with rhodium by weight percentage;
The content of alkyl iodide in reaction system is 5%-18% by weight percentage;
The concentration of water is 4%-6% by weight percentage;
The concentration of hydroiodic acid is 0.2%-0.4% by weight percentage;
The concentration of alkali metal salt compounded of iodine is 7%-12% by weight percentage;
The mol ratio of sulfonate and rhodium salt is 1-100;
Said sulfonate is LiHSO
3, NaHSO
3, KHSO
3, Zn (HSO
3)
2, NH
4HSO
3Or their salt that contains the crystallization water.
2. the catalyst system of synthesizing acetic acid by methanol low-pressure carbonylation according to claim 1 is characterized in that, used rhodium salt is: RhCl
3, RhBr
3, RhI
3, Rh (OAc)
2, [Rh (CO)
2Cl]
2, [Rh (CO)
2Br]
2Or [Rh (CO)
2I]
2
3. the catalyst system of synthesizing acetic acid by methanol low-pressure carbonylation according to claim 1 is characterized in that, used alkyl iodide is an iodomethane.
4. the catalyst system of synthesizing acetic acid by methanol low-pressure carbonylation according to claim 1 is characterized in that, used alkali metal salt compounded of iodine is a lithium iodide.
5. the catalyst system of synthesizing acetic acid by methanol low-pressure carbonylation according to claim 1 is characterized in that, when catalyzed carbonylation prepared acetic acid, reactant was a methyl alcohol.
6. the catalyst system of synthesizing acetic acid by methanol low-pressure carbonylation according to claim 1 is characterized in that, used polar solvent is an acetic acid, and its consumption is the 10-120% of reaction-ure mixture by weight.
7. the catalyst system of synthesizing acetic acid by methanol low-pressure carbonylation according to claim 1 is characterized in that, when catalyzed carbonylation prepared acetic acid, reaction temperature was 160-190 ℃, and reaction pressure is 2.8-3.2MPa, and the reaction time is 0.1-0.5 hour.
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